US9080069B2 - Composition for inkjet and recording material - Google Patents

Composition for inkjet and recording material Download PDF

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Publication number
US9080069B2
US9080069B2 US13/738,396 US201313738396A US9080069B2 US 9080069 B2 US9080069 B2 US 9080069B2 US 201313738396 A US201313738396 A US 201313738396A US 9080069 B2 US9080069 B2 US 9080069B2
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Prior art keywords
composition
inkjet
metal powder
group
inkjet according
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US13/738,396
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US20130196127A1 (en
Inventor
Naoyuki Toyoda
Masaya Shibatani
Minoru Yamada
Tomohiro Ogawa
Hidekazu Moriyama
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Seiko Epson Corp
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Seiko Epson Corp
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Assigned to SEIKO EPSON CORPORATION reassignment SEIKO EPSON CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MORIYAMA, HIDEKAZU, YAMADA, MINORU, OGAWA, TOMOHIRO, SHIBATANI, MASAYA, TOYODA, NAOYUKI
Publication of US20130196127A1 publication Critical patent/US20130196127A1/en
Priority to US14/612,729 priority Critical patent/US9416288B2/en
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Publication of US9080069B2 publication Critical patent/US9080069B2/en
Priority to US15/207,928 priority patent/US10053590B2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/14—Printing inks based on carbohydrates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24909—Free metal or mineral containing

Definitions

  • the present invention relates to a composition for inkjet and a recording material.
  • an inkjet method As a recording method to a recording medium by using compositions including pigments or colorants, an inkjet method is used.
  • the inkjet method provides excellent formation of the fine pattern and also, it is appropriate to perform an application to the curve surface part.
  • the composition composition for inkjet
  • the coloring agent pigments or colorants
  • an organic solvent is used so that it has advantages such that the thickness of a print layer becomes smaller, and it can be prevented from an occurrence of unnecessary roughness (see, for example, Japanese Laid-Open Patent Publication No. 2010-18730).
  • the object of the present invention is to provide the composition for inkjet with excellent discharge stability and excellent storage stability and to provide the composition for inkjet which can be appropriately used to form a pattern (printing part) with excellent glossy appearance. Also, the object of the present invention is to provide a recording material having a pattern with excellent glossy appearance by using the composition for inkjet.
  • the composition for inkjet in the present invention is discharged by the inkjet method.
  • the composition for inkjet comprises a metal powder, an organic solvent, and a binder resin; and wherein the metal powder is treated by a surface preparation with a fluorinated silane compound and/or a fluorinated phosphate ester as a surface preparation agent. Because of this, the composition for inkjet can be provided with excellent discharge stability and excellent storage stability, and it can be appropriately used for producing a recording material having a pattern (printing part) with excellent glossy appearance.
  • the composition for inkjet of the present invention it is preferable that in the metal powder, at least vicinity surface of the powder mainly constitutes A1 and the surface is treated by a surface preparation with the fluorinated silane compound and/or the fluorinated phosphate ester.
  • A1 originally has excellent glossy appearance, but the present inventors have discovered problems such that when the powder constituting A1 was used for the composition for inkjet, the storage stability of the composition for inkjet became low significantly and the deterioration of the discharge stability occurred because the viscosity was increased by the gelation.
  • the present invention even when the powder constituting A1 on the surface is used, the occurrence of the above problems can be properly prevented. That is, the effect of the present invention is significantly demonstrated when the composition for inkjet includes the metal powder and at least the surface of the powder mainly constituting A1 is treated by the fluorinated silane compound and/or the fluorinated phosphate ester.
  • the metal powder has a scale-like shape. Because of this, the recording material produced by using the composition for inkjet can be provided with particular excellent glossy appearance and particular excellent abrasion resistance.
  • the composition for inkjet preferably includes the metal powder that is treated by the surface preparation with the fluorinated silane compound having a chemical formula shown in formula (1) below.
  • R 1 SiX 1 a R 2 (3-a) (1) (In formula (1), R 1 represents a hydrocarbon group in which a part or all of hydrogen atoms is substituted by fluorine atom, X 1 represents hydrolysis group, ether group, chloro group or hydroxyl group, R 2 represents alkyl group having a carbon number 1 to 4, and a represents an integer between 1 to 3.) Because of this, the composition for inkjet can be provided with particular excellent discharge stability and particular excellent storage stability, and the recording material produced by using the composition for inkjet can be provided with particular excellent glossy appearance and particular excellent abrasion resistance.
  • the composition for inkjet preferably includes the metal powder that is treated by the surface preparation with the fluorinated phosphate ester having a chemical formula shown in formula (2) below.
  • POR n (OH) 3-n (2) (In formula (2), R represents CF 3 (CF 2 ) m —, CF 3 (CF 2 ) m (CH 2 ) l —, CF 3 (CF 2 ) m (CH 2 O) l —, CF 3 (CF 2 ) m (CH 2 CH 2 O) l —, CF 3 (CF 2 ) m O— or CF 3 (CF 2 ) m (CH 2 ) l O—, n represents an integer between 1 to 3, m represents an integer between 2 to 18, and l represents an integer between 1 to 18.) Because of this, the composition for inkjet can be provided with particular excellent discharge stability and particular excellent storage stability, and the recording material produced by using the composition for inkjet can be provided with particular excellent glossy appearance and particular excellent abrasion resistance.
  • the surface preparation agent has a perfluoroalkyl structure. Because of this, the composition for inkjet is further secured with excellent discharge stability and excellent storage stability, and the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance and excellent abrasion resistance.
  • the average grain diameter of the metal powder is more than 500 nm and less than 3.0 ⁇ m. Because of this, the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance and excellent high-class appearance. Also, the composition for inkjet can be provided with excellent storage stability and excellent discharge stability.
  • the organic solvent preferably includes at least one compound selected from alkylene glycol compounds and lactone compounds. Because of this, the composition for inkjet has particular excellent storage stability and particular excellent discharge stability. Also, since the solvent was promptly removed from the composition for inkjet immediately after discharging by the inkjet method, it can be provided with particular excellent productivity of the recording material.
  • the composition for inkjet preferably further includes at least one selected from silicone-based surfactants, polyoxyethylene-based surfactants, and acethylenic diol-based surfactants. Because of this, the composition for inkjet can be provided with particular excellent storage stability and particular excellent discharge stability. Also, the arrangement (sequence) of the metal powder on the recording material can be appropriate so that the recording material can be provided with a particular excellent glossy appearance and particular excellent abrasion resistance.
  • the binder resin preferably includes a compound having a cellulose backbone. Because of this, the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance and excellent abrasion resistance.
  • the binder resin preferably includes at least one selected from a group comprising cellulose acetate butyrate, nitrocellulose, and ethylcellulose. Because of this, the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance and excellent abrasion resistance.
  • the recording material of the present invention is produced by imparting the composition for inkjet on a recording medium. Because of this, the recording material having a pattern (printing part) with excellent glossy appearance and excellent abrasion resistance can be provided.
  • the composition for inkjet of the present invention is discharged by the inkjet method and includes a metal powder, an organic solvent, and a binder resin (binder).
  • an inkjet method is used as a recording method for a recording medium by using compositions including pigments or colorants.
  • the inkjet method can be provided with excellent fine pattern of a formation and it is appropriate to perform the application to the curve surface part.
  • the composition (inkjet composition) that the coloring agent (pigments or colorants) was dispersed or dissolved in an organic solvent is used because it has advantages such that the thickness of a print layer becomes smaller, and an occurrence of unnecessary roughness can be prevented.
  • the composition for inkjet of the present invention includes the metal powder, and the metal powder is treated by the surface preparation with the fluorinated silane compound and/or the fluorinated phosphate ester as a surface preparation agent. Because of this, in the composition for inkjet, it can be provided with excellent chemical stability and excellent dispersal stability.
  • the metal powder can be appropriately arranged on the peripheral outer surface of the printing part so that the glossy appearance, which is originally included in a character of the metal material constituting the metal powder, can be sufficiently demonstrated. Also, even when the organic solvent, which has low surface tension, is used as the constituent material of the composition for inkjet, in the recording material produced by the composition for inkjet, the metal powder can be properly arranged (leafing) on the peripheral outer surface of the printing part so that the glossy appearance, which is originally included in a character of the metal material constituting the metal powder, can be sufficiently demonstrated.
  • the selection of the organic solvent can be widened and without losing the glossy appearance which is originally included as a characteristic of the metal material, it can be easily adjusted the characteristics of the composition for inkjet and the characteristics of the recording material produced by using the composition for inkjet (for example, viscosity of the composition for inkjet, storage stability, discharge stability, abrasion resistance of the recording material, or the like).
  • the composition for inkjet of the present invention includes the metal powder that is treated by the surface preparation with the fluorinated silane compound and/or the fluorinated phosphate ester as the surface preparation agent.
  • the mother particles constituting the metal particles are constituted by at least a metal material in a region including the vicinity of the surface.
  • the region could be constituted by the metal material, and also, it can be possible to have a base portion formed by non-metallic material and a coated film formed by the metallic material to coat the base portion.
  • a metal material constituting mother particles a metal or various alloys as elemental substances can be used but it is preferable that the mother particles are mainly constituted by A1 on at least vicinity of the surface.
  • A1 has a particular excellent glossy appearance, but when the powder constituted by A1 applied to the composition for inkjet, the storage stability of the composition became low particularly, and the present inventors have discovered a problem such as the deteriorate of the discharge stability caused by increasing the viscosity because the gelatinization was significantly generated.
  • the present invention even when the powder constituted by A1 on the surface is used, the occurrence of the above described problem can be reliably prevented.
  • the powder constituted by A1 is treated by the surface preparation with the surface preparation agent (fluorinated silane compound and/or fluorinated phosphate ester) so that the effect of the present invention is significantly demonstrated.
  • the surface preparation agent fluorinated silane compound and/or fluorinated phosphate ester
  • the mother particles can be produced by any method, but when it is constituted by A1 , the vapor deposition method can be used to form a film constituted by A1 and after that, it is preferable to obtain the powder by crushing the film.
  • the glossy appearance which is originally included in a characteristic of A1 can be effectively appeared in a pattern (printing part) formed by using the composition for inkjet of the present invention.
  • the variability of the characteristics within the particles can be suppressed.
  • the relatively-thin metal powder can be produced appropriately.
  • the mother particles When the mother particles are produced by using this type of method, for example, by forming a film (film formation) constituted by A1 on the base material, the mother particles can be produced appropriately.
  • a base material for example, a plastic film such as polyethylene terephthalate, or the like can be used.
  • the base material can be included a parting agent layer on the surface of the film formation.
  • the crushing film is performed in liquid by giving supersonic vibration to the film.
  • alcohol compounds such as methanol, ethanol, propanol, butanol, carbon hydride compounds such as n-heptane, n-octane, decane, dodecane, tetra-decane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylebenzene, ether compounds such as ethyl glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methylethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, tripropylene glycol dimethyl ether, triethylene glycol n-butyl ether, triethylene glycol n
  • the metal powder related to the present invention is treated by the surface preparation with fluorinated silane compound and/or fluorinated phosphate ester as the surface preparation agent.
  • fluorinated silane compound a silane composition having at least one fluorine atom within a molecule can be used.
  • the fluorinated silane composition as the surface preparation agent has a chemical formula shown in formula (1) below.
  • R 1 represents a hydrocarbon group in which a part or all of hydrogen atoms is substituted by fluorine atom
  • X 1 represents hydrolysis group, ether group, chloro group or hydroxyl group
  • R 2 represents alkyl group having a carbon number 1 to 4, and a represents an integer between 1 to 3.
  • the composition for inkjet can be provided with excellent discharge stability and excellent storage stability, and a printing part of the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance and excellent abrasion resistance.
  • R 1 in formula (1) for example, it can be alkyl group, alkenyl group, aryl group, aralkyl group in which a part or all of hydrogen atoms are substituted by fluorine atom.
  • hydrogen atoms hydrogen atoms which are not substituted by fluorine atom
  • the molecular configuration can be substituted by amino group, carboxyl group, hydroxyl group, thiol group or the like, and hetero atom or benzene of aromatic ring such as —O—, —S—, —NH—, —N ⁇ can intervene within a carbon chain.
  • R 1 the concrete examples of R 1 are that a part or all of hydrogen atoms are substituted by fluorine atoms in phenyl group, benzyl group, phenethyl group, hydroxyphenyl group, chlorophenyl group, aminophenyl group, naphthyl group, anthranil group, pyrenyl group, thienyl group, pyrrolyl group, cyclohexyl group, cyclohexenyl group, cyclopentyl group, cyclopentenyl group, pyridinyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, octadecyl group, n-octyl group, chloromethyl group, methoxyethyl group, hydroxyethyl group, aminoethyl group
  • the fluorinated silane compound shown in formula (1) it is preferable to include a composition having a configuration that a part or all of hydrogen atoms in a silane compound are substituted by fluorine atoms.
  • the silane compounds are dimethyl dimethoxy silane, diethyl diethoxy silane, 1-propenyl methyl dichlorosilane, propyl dimethyl chlorosilane, propylmethyl dichlorosilane, propyl trichlorosilane, propyl triethoxysilane, propyl trimethoxysilane, styrylethyl trimethoxysilane, tetradecyl trichlorosilane, 3-thiocyanate propyl triethoxysilane, p-tolyl dimethylchlorosilane, p-tolyl methyl dichlorosilane, p-tolyl trichlorosilane, p-tolyl trim
  • the fluorinated silane compound (surface preparation agent) has a perfluoroalkyl structure (CnF 2n+1 ). Because of this, the composition for inkjet can be provided with excellent discharge stability and excellent storage stability, and a printing part of the recording material produced by using the composition for inkjet can be produced with excellent glossy appearance and excellent abrasion resistance.
  • CnF 2n+1 As a fluorinated silane compound having a perfluoroalkyl structure (CnF 2n+1 ), for example, it can be shown in formula (3) below.
  • X 1 represents hydrolysis group, ether group, chloro group or hydroxyl group
  • R 2 represents alkyl group having a carbon number 1 to 4
  • n represents an integer between 1 to 14
  • m represents an integer between 2 to 6
  • a represents an integer between 1 to 3.
  • the concrete examples of the compounds having such a structure are CF 3 —CH 2 CH 2 —Si(OCH 3 ) 3 , CF 3 (CF 2 ) 3 —CH 2 CH 2 —Si(OCH 3 ) 3 , CF 3 (CF 2 ) 5 —CH 2 CH 2 —Si(OCH 3 ) 3 , CF 3 (CF 2 ) 5 —CH 2 CH 2
  • fluorinated silane compound it is also possible to use a perfluoroether structure (C n F 2n+1 O) instead of perfluoroalkyl structure (C n F 2n+1 ).
  • a fluorinated silane compound having a perfluoroether structure (C n F 2n+1 O) for example, it can be shown in formula (4) below.
  • the concrete examples of the compounds having such a structure are CF 3 O(CF 2 O) 6 —CH 2 CH 2 —Si(OC 2 H 5 ) 3 , CF 3 O(C3F6O) 4 —CH 2 CH 2 —Si(OCH 3 ) 3 , CF 3 O(C3F6O) 2 (CF 2 O) 3 —CH 2 CH 2 —Si(OCH 3 ) 3 , CF 3 O(C3F6O) 8 —CH 2 CH 2 —Si(OCH 3 ) 3 , CF 3 O(C4F9O) 5 —CH 2 CH 2 —Si(OCH 3 ) 3 , CF 3 O(C4F9O) 5 —CH 2 CH 2 —Si(CH 3 )(OC 2 H 5 ) 2 , CF 3 O(C3F6O) 4 —CH 2 CH 2 —Si(C 2 H 5 )(OCH 3 ) 2 .
  • a fluorinated phosphate ester As the fluorinated phosphate ester, a phosphate ester having at least one fluorine atom within a molecule can be used. Specifically, it is preferable that the fluorinated phosphate ester as the surface preparation agent has a chemical formula shown in formula (2) below.
  • R represents CF 3 (CF 2 ) m —, CF 3 (CF 2 ) m (CH 2 ) 1 —, CF 3 (CF 2 ) m (CH 2 O) 1 —, CF 3 (CF 2 ) m (CH 2 CH 2 O) 1 —, CF 3 (CF 2 ) m O— or CF 3 (CF 2 ) m (CH 2 ) 1 O—, n represents an integer between 1 to 3, m represents an integer between 2 to 18, and l represents an integer between 1 to 18.
  • the composition for inkjet can be provided with particular excellent discharge stability and particular excellent storage stability, and a printing part of the recording material produced by using the composition for inkjet can be provided with a particular excellent glossy appearance and particular excellent abrasion resistance.
  • m is an integer between 3 to 14, but an integer between 4 to 12 is more preferable.
  • the fluorinated phosphate ester (surface preparation agent) has (C n F 2n+1 ). Because of this, the composition for inkjet can be provided with excellent discharge stability and excellent storage stability, and a printing part of the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance and excellent abrasion resistance.
  • the above surface preparation agent fluorinated silane compound, fluorinated phosphate ester
  • an acid for example, it can be proton acid of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, hyposulfurous acide, nitrous acid, hyponitrous acid, phosphorous acid, and hypophosphorous acid, or the like.
  • hydrochloric acid, phosphoric acid, and acetic acid can be preferable.
  • a base for example, sodium hydrate, potassium hydrate, calcium hydrate, or the like can be used. Among them, sodium hydrate and potassium hydrate can be preferable.
  • the shape of the metal powder can be spherical shape, spindle shape, needle-shape, or the like, but scale like-shape can be preferable. Because of this, on the recording medium that the composition for inkjet is applied, a main surface of metal powder can be arranged along a surface shape of the recording medium so that the metal material constituting the metal powder, which is originally provided with glossy appearance or the like, can be more effectively demonstrated in an obtained recording medium. Also, the formed pattern (printing part) can be provided with excellent glossy appearance and excellent high-class appearance, and also, the recording material can be provided with excellent abrasion resistance.
  • the surface preparation is not provided by the fluorinated silane compound and/or the fluorinated phosphate ester and the metal powder has scale-like shape, it significantly tends to become lower storage stability and discharge stability of the composition for inkjet.
  • the metal powder has scale-like shape, the occurrence of this type of problem can be absolutely prevented. That is, when the shape of the metal powder is scale-like, the effect of the present invention is significantly demonstrated.
  • the scale-like shape is defined that an area as viewed from a predetermined angle (as viewed in a planar view) is bigger shape than an area as viewed in a direction perpendicular to an observation direction such as a plated-form or a curved plated-form.
  • a ratio between an area S 1 ( ⁇ m 2 ) as viewed in a direction observed from where a profile area becomes maximum and an area S 0 ( ⁇ m 2 ) as viewed in a direction observed from where an area as viewed in a direction perpendicular to an observation direction becomes maximum is preferably more than 2, and more preferably more than 5, and further preferably more than 8.
  • this value can be obtained by performing the observation for any 10 particles and averaging the calculated values for these particles.
  • the average grain diameter of the metal powder is preferably more than 500 nm and less than 3.0 ⁇ m and more preferably more than 800 nm and less than 1.8 ⁇ m. Because of this, the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance and excellent high-class appearance. Also, the composition for inkjet can be provided with excellent storage stability and excellent discharge stability.
  • the content rate of the metal powder in the composition for inkjet is preferably more than 0.5 mass % and less than 10.0 mass %, and more preferably, more than 1.0 mass % and less than 5.0 mass %.
  • the organic solvent has a function to disperse the metal powder in the composition for inkjet. And, the organic solvent is removed (vaporized) in the production process of the recording material.
  • a boiling point of the organic solvent under one atmospheric pressure is preferably more than 100° C. and less than 300° C., and more preferably more than 150° C. and less than 250° C. Because of this, it can sufficiently provide excellent productivity of the recording material that the composition for inkjet is used. Also, particular excellent stability of the composition when the composition for inkjet is stored and particular excellent discharge stability can be provided.
  • organic solvent it can be anything if the organic solvent is a liquid form in the environment usage of the composition for inkjet (for example, under at normal temperature (20° C.) and at normal pressure (one atmospheric pressure)), but for example, alcohol compounds (methyl alcohol, ethyl alcohol, propylene alcohol, butyl alcohol, monovalent alcohol such as isobutyl alcohol and ethylene glycol, multivalent alcohol such as glycerin, fluoride of these compounds, or the like), ketone compounds (acetone, methylethyl ketone, cyclohexanone, or the like), carboxylic acid ester compounds (methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, or the like), ether compounds (diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, or the like), lactone compounds, or the like can be used.
  • alcohol compounds
  • the composition for inkjet preferably includes at least one compound selected from alkylene glycol compounds and lactone compounds. Because of this, the composition for inkjet can be provided with particular excellent storage stability and particular excellent discharge stability. Also, since the solvent can be promptly removed after discharging by the inkjet method, particular excellent productivity of the recording material can be provided.
  • alkylene compounds that can be used as an organic solvent for example, it can be alkylene glycol such as ethylene glycol and propylene glycol, compounds that at least one hydroxyl group in the alkylene glycol is etherified or esterified, or the like.
  • alkylene glycol part of the alkylene glycol compounds it can be ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, or the like.
  • alkylene glycol monoether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, or the like.
  • alkylene glycol diether are ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, or the like.
  • the lactone compounds that can be used as an organic solvent can be ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, or the like.
  • the organic solvent preferably includes at least one or two selected from a group comprising diethylene glycol dimethyl ether, diethylene glycol diethyle ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dibutyl ether, and ⁇ -butyrolactone. Because of this, the composition for inkjet can be provided with excellent storage stability and excellent discharge stability.
  • the recording material can be provided with excellent glossy appearance and excellent high-class appearance.
  • the content rate of the organic solvent in the composition for inkjet is preferably more than 70 mass % and less than 99 mass %, and more preferably more than 80 mass % and less than 98 mass %. Because of this, the composition for inkjet can be provided with excellent storage stability and excellent discharge stability, and the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance.
  • the composition for inkjet can include more than two compositions as an organic solvent. In this case, it is preferable that the sum of the content rates of these compounds is in a range of the values as described above.
  • Binder Resin (Binder) Binder Resin (Binder)
  • the binder resin has a function to improve adhesiveness of the metal powder to the recording material. Because of this, the recording material can be provided with excellent durability (abrasion resistance, water resistance).
  • a binder resin constituting the composition for inkjet for example, it can be acrylic resin, styrene-acrylic resin, rosin modified resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, cellulose-based resin (for example, cellulose acetate butyrate, hydroxypropyl cellulose), polyvinyl butyral, polyvinyl alcohol, polyurethane, or the like.
  • the composition for inkjet preferably includes a compound having a cellulose backbone. Because of this, the recording material produced by using the composition for inkjet can be provided with a particular excellent glossy appearance and particular excellent abrasion resistance.
  • a binder resin a compound having a cellulose backbone
  • the binder resin can be dispersed or dissolved in the organic solvent.
  • the content rate of the binder resin (binder) in the composition for inkjet is preferably more than 0.1 mass % and less than 5.0 mass %, and more preferably more than 0.5 mass % and less than 2.0 mass %. Because of this, the composition for inkjet can be sufficiently provided with excellent storage stability and excellent discharge stability, and the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance, excellent abrasion resistance, or the like.
  • the composition for inkjet can include more than two compounds as a binder resin. In this case, it is preferable that the sum of the content rates of these compounds is preferably in a range of the values as described above.
  • the composition for inkjet preferably includes at least one selected from silicone-based surfactant, polyoxyethylene-based surfactant, and acetylene diol. Because of this, the composition for inkjet can be provided with particular excellent storage stability and particular excellent discharge stability. Also, the arrangement (sequence) of the metal powder on the recording material can be appropriate, and the recording material can be provided with excellent glossy appearance and excellent abrasion resistance.
  • silicone-based surfactant for example, polyether-modified silicone (BYK-300, 306, 307; BYK Japan KK, KF-6011, 6012, 6017, 6015, 6043; Shin-Etsu Silicone Co., Ltd.), polyester-modified silicone (BYK-313, 315; BYK Japan KK), polyether-modified silicone acrylate-terminated (BYK-3500, 3510, 3530; BYK Japan KK), polyester-modified silicone acrylate-terminated (BYK-3570; BYK Japan KK), polyglycerol-modified silicone (KF-6100, 6104; Shin-Etsu Silicone Co., Ltd.), aminopropyl-modified silicone (KF-8015, 8020; Shin-Etsu Silicone Co., Ltd.), amino-modified silicone (KF-8004, 867S; Shin-Etsu Silicone Co., Ltd.), or the like can be used.
  • polyether-modified silicone BY
  • polyoxyethylene-based surfactant for example, it can be polyoxyethylene alkylether such as polyoxyethylene cetyl ether (e.g., Nissan Nonion P-208; NOF Corporation), polyoxyethylene oleyl ether (e.g., Nissan Nonion E-2025, E-205S; NOF Corporation), or polyoxyethylene lauryl ether (e.g., Emulgen 106, 108; Kao Corporation), polyoxyethylene alkylphenol ethers such as polyoxyethylene octylphenol ether (e.g., Nissan Nonion HS-204, HS-206, HS-208; NOF Corporation), sorbitan monoester such as sorbitan monocaprylate (e.g., Nissan Nonion CP-08R; NOF Corporation), or sorbitan monolaurate (e.g., Nissan Nonion LP-20R, NOF Corporation), polyoxyethylene sorbitan monoester such as polyoxyethylene sorbitan monostearate (
  • acetylene diol for example, Surfynol 104, 82, 465, 485, or TG (all available from Air Products and Chemicals Inc.), Olfine STG, Olfine E1010 (these are the trade name of Nissin Chemical Industry Co., Ltd.), or the like can be used.
  • the content rate of the above described surfactants in the composition for inkjet is preferably more than 0.01 mass % and less than 5.0 mass %, and more preferably more than 0.1 mass % and less than 2.0 mass %. Because of this, the composition for inkjet can be provided with excellent storage stability and excellent discharge stability, and the recording material produced by using the composition for inkjet can be provided with excellent glossy appearance, or the like.
  • the composition for inkjet can include more than two compounds as surfactants as described above. In this case, it is preferable that the sum of the content rates of these compounds is in a range of the values as described above.
  • composition for inkjet of the present invention can include components (other components) besides the components discussed above.
  • these components for example, it can be slip agents (leveling agents), dispersants, penetration enhancers, a pH adjusters, coloring agents (pigment, colorant), matting agents, waxes, antifungal agents, preservatives, antioxidants, chelating agents, thickeners, sensitizer (sensitizing dye), or the like.
  • the composition for inkjet includes a slip agent
  • a slip agent it is not particularly limited, but for example, silicone surfactants of polyester modified-silicone, polyether modified-silicone, or the like can be used and it is preferable to use polyester modified-polydimethylsiloxane or polyether modified-polydimethylsiloxane.
  • the viscosity of the composition for inkjet in the present invention at room temperature (20° C.) is preferably less than 20 mPa ⁇ s and more preferably more than 3 mPa ⁇ s and less than 15 mPa ⁇ s. Because of this, the ink droplet by the inkjet method can be properly performed.
  • the recording material of the present invention is produced by imparting the above described composition for inkjet onto the recording medium.
  • Such a recording material has a pattern (printing part) with excellent glossy appearance.
  • the recording material of the present invention can be anything, but for example, papers (regular paper, exclusive paper, or the like), plastic materials such as vinyl chloride and propylene carbonate can be appropriately used.
  • the recording material of the present invention can be used for any purpose, and for example, it can be used for a decoration product or other purpose.
  • it can be interior decorations for vehicles such as a console lid, a switch-base, a center cluster, an interior panel, an emblem, a center console, an indicator face plate, or the like.
  • it can be indicators such as a control part (type of key switch) of various electric devices, a decorative part demonstrating decorative characteristics, a guidepost, a logo, or the like.
  • a piezo method As a droplet discharge method (inkjet method), a piezo method, a method that discharges ink from bubble generated by heating ink, or the like can be used, but from the viewpoint of the prevention of a property change in the composition for inkjet, the piezo method is preferable.
  • a publicly known droplet discharge device can be used for performing the discharge of the composition for inkjet by using the inkjet method.
  • the composition for inkjet discharging to the recording material by the inkjet method loses fluidity in the formed printing part so that the formation becomes stabilized.
  • a decompression treatment or a heating treatment can be used. Because of this, the efficiency of the organic solvent can be improved and excellent productivity of the recording material can be provided.
  • silicone oil entirely applies to one side of the film surface.
  • a film constituting A1 is formed on the surface, that the silicone oil was applied, by the evaporation method.
  • the film made by polyethylene terephthalate (base material), which constitutes the A1 film is soaked into the liquid constituted by diethylene glycol diethylester and the supersonic vibration is applied to it. Because of this, the powder made by A1 that has scale-like shape (particles that should become mother particles) was obtained.
  • the above obtained A1 particles were put in 1 mass % propanol solution of CF 3 (CF 2 ) 4 (CH 2 ) 2 O —PO(OH) 2 as the fluorinated phosphate ester and by stirring it for 10 seconds, the surface preparation was performed by the fluorinated phosphate ester so that the metal powder was obtained.
  • the average grain diameter of the obtained metal powder is 0.8 ⁇ m, and the average thickness is 60 nm.
  • the metal powder was mixed with diethylene glycol diethyl ether, ⁇ -butyrolactone, tetraethylene glycol dimethyl ether, and tetraethylene glycol dibutyl ether as an organic solvent, cellulose acetate butyrate as a binder resin (binder), and BYK-3500 (BYK Chemie Company) as a silicone-based surfactant so that the composition for inkjet was obtained.
  • the constitution of the metal particles (types of the compounds (fluorinated compound) used for the composition of the mother particles and the surface preparation) is shown in table 1.
  • the compositions for inkjet in these examples were produced in the same manner as the above described example 1 besides being the compositions as shown in table 1 by changing the types of raw materials and ratios used for preparing the compositions for inkjet.
  • composition for inkjet was produced in the same manner as the above described example 1 besides particles made by A1, which were not treated by the surface preparation, used as a metal powder.
  • composition for inkjet was produced in the same manner as the above described comparative example 1 besides using a spherical shape of the A1 powder (not treated by the surface preparation) as a metal powder produced by using a gas atomization method.
  • composition for inkjet was produced in the same manner as the above described example 1 besides obtaining the metal powder treated by the surface preparation using NH 3 —(CH 2 ) 3 —Si(OCH 3 ) 3 , which is not fluorinated silane composition and fluorinated phosphate ester, instead of CF 3 (CF 2 ) 4 (CH 2 ) 2 O—PO(OH) 2 as fluorinated phosphate ester.
  • composition for inkjet was produced in the same manner as the above described example 1 besides obtaining the metal powder treated by the surface preparation using stearic acid, which is not fluorinated silane composition and fluorinated phosphate ester, instead of CF 3 (CF 2 ) 4 (CH 2 ) 2 O—PO(OH) 2 as fluorinated phosphate ester.
  • composition for inkjet was produced in the same manner as the above described example 1 besides obtaining the metal powder treated by the surface preparation using oleic acid, which is not fluorinated silane composition and fluorinated phosphate ester, instead of CF 3 (CF 2 ) 4 (CH 2 ) 2 O—PO(OH) 2 as fluorinated phosphate ester.
  • the components of the compositions for inkjet as a whole are shown in table 1.
  • “A1” represents CF 3 (CF 2 ) 4 (CH 2 ) 2 O—PO(OH) 2
  • “A2” represents CF 3 (CF 2 ) 7 —CH 2 CH 2 —Si(OCH 3 ) 3
  • “A3” represents CF 3 (CF 2 ) 5 —CH 2 CH 2 —Si(OC 2 H 5 ) 3
  • “A4” represents CF 3 —CH 2 CH 2 —Si(OCH 3 ) 3
  • “A′1” represents NH 3 —(CH 2 ) 3 —Si(OCH 3 ) 3
  • “A′2” represents stearic acid
  • “A′3” represents oleic acid
  • “DEGDEE” represents diethylene glycol diethyl ether
  • “DEGDME” represents diethylene glycol dimethyl ether
  • “TEGDME” represents tetraethylene glyco
  • the components of the constituent materials of the mother particles are shown as a ratio by weight for the content rates of respective elements. Also, by performing the observation of any 10 particles included in respective compositions for inkjet, the ratios (S 1 /S 0 ) between an area S 1 ( ⁇ m 2 ) (as viewed in a planer view) as viewed in a direction observed from where a profile area becomes maximum and an area S 0 ( ⁇ m 2 ) as viewed in a direction observed from where an area as viewed in a direction perpendicular to an observation direction becomes maximum are calculated and these average values are show in table 1.
  • the viscosity of the compositions for inkjet in respective examples measured in reference with J1S Z8809 at 20° was in a range between 3 mPa ⁇ s and 15 mPa ⁇ s, respectively.
  • a droplet discharge device equipped in a chamber (thermal chamber) and the compositions for inkjet in the respective examples and comparative examples as described above were prepared.
  • the respective compositions for inkjet were dropped 2000000 times (2000000 drops) from each nozzle of the droplet discharge heads under the environment of 25° C., 55% RH so the sequence discharge of droplet was performed.
  • the droplet discharge device was turned off, and it was left for 240 hours in a condition that the respective inkjet compositions were filled in a flow channel of the droplet discharge device under the environment of 25° C., 55% RH.
  • the droplet was sequentially performed 4000000 times (4000000 drops) from each nozzle of the droplet discharge heads under the environment of 25° C., 55% RH. After it was left for 150 hours, regarding the droplets of 4000000 times discharged from the nozzles specified in a peripheral central part of the droplet discharge heads, an average value of shift amount d, which was shifted from a central position that the respective droplets were targeted to land, was calculated so that the evaluation was made in accordance with 5 stages standard below. As this value becomes smaller, it can be said that an occurrence of a flying curve was prevented.
  • D the average of shift amount d is more than 0.17 ⁇ m and less than 0.21 ⁇ m.
  • a droplet discharge device equipped in a chamber (thermal chamber) and the compositions for inkjet in the respective examples and comparative examples as described above were prepared.
  • the droplet discharge was performed by changing the frequency of vibration (frequency) of the piezo-elements in all nozzles of the droplet discharging heads under the environment of 25° C., 55% RH.
  • the droplet discharge time in the frequency was 10 minutes.
  • a frequency that numbers of non-discharged nozzles were less than 1% in all nozzle numbers is an actual usable maximum frequency so that the evaluation was made in an actual usable frequency range in accordance with 4 stages standard below. As this value becomes larger, it has an excellent frequency property.
  • A more than 15 kHz.
  • A the percentage of rise of viscosity is less than 5%.
  • an interior panel as a recording material was provided as follows. First of all, the compositions for inkjet were put in the inkjet apparatus. After that, the compositions for inkjet were discharged in a predetermined patter on a base material (recording medium) having a curved surface part formed by using the solvent inkjet media (IJS-RC-YF170; made by Mitsubishi Paper Mills Ltd.). After that, the organic solvent was removed by the heat treatment in a condition of 60° C. for 30 seconds so that an interior panel as a recording material was obtained. By using the above described method and by using the compositions for inkjet of the respective examples and the comparative examples, 10 interior panels (recording materials) were provided, respectively.
  • the solvent inkjet media IJS-RC-YF170
  • the abrasion resistance test using polyethylene terephthalate film was performed by using Sutherland rub tester in reference with JIS K5701 when 48 hours elapsed from the production of the recording materials.
  • the degree of glossiness (flap angle 60°) for the recording materials was measured after the abrasion resistance test, and a decreasing rate of the degree of glossiness after the abrasion resistance test was calculated for the evaluation in accordance with standards below.
  • a decreasing rate of the degree of glossiness is less than 8%.
  • a decreasing rate of the degree of glossiness is more than 8% and less than 16%.
  • a decreasing rate of the degree of glossiness is more than 16% and less than 26%.
  • a decreasing rate of the degree of glossiness is more than 26% and less than 33%.
  • a decreasing rate of the degree of glossiness is less than 33% or the surface of the recording medium is exposed because the metal particles were come off.
  • the compositions for inkjet in the present invention had excellent discharge stability of droplet and excellent storage stability. Also, the recording materials of the present invention had excellent glossy appearance, and the pattern forming parts had excellent abrasion resistance. On the other hand, the sufficient results were not obtained in the comparative examples.

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JP5978637B2 (ja) 2012-02-01 2016-08-24 セイコーエプソン株式会社 インクジェット用組成物、記録物の製造方法および記録物
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JP6999087B2 (ja) * 2017-01-11 2022-02-04 セイコーエプソン株式会社 溶剤系インク組成物
JP7077716B2 (ja) * 2018-03-29 2022-05-31 セイコーエプソン株式会社 インクジェット用組成物および記録物
JP2019172862A (ja) * 2018-03-29 2019-10-10 セイコーエプソン株式会社 インクジェット用組成物および記録物
JP2020128021A (ja) * 2019-02-07 2020-08-27 セーレン株式会社 成形体
JP7380032B2 (ja) * 2019-09-30 2023-11-15 セイコーエプソン株式会社 インクジェット用インクセットおよび記録方法
JP7380031B2 (ja) * 2019-09-30 2023-11-15 セイコーエプソン株式会社 インクジェット用組成物
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